title: Electronic properties of CuPc and H2Pc: an experimental and theoretical study.
abstract: Phthalocyanine (H2Pc) and its open-shell copper complex (CuPc) deposited on amorphous gold films have been studied by combining the outcomes of several synchrotron based spectroscopic tools (X-ray photoelectron spectroscopy, UV photoelectron spectroscopy and near-edge X-ray absorption fine structure, NEXAFS, spectroscopy) with those of density functional theory (DFT) calculations. The assignment of experimental evidence has been guided by the results of DFT numerical experiments carried out on isolated molecules. With specific reference to CuPc NEXAFS data collected at the N K-edge, they have been assigned by using the open-shell time-dependent DFT (TDDFT) in the framework of the zeroth order regular approximation (ZORA) scalar relativistic approach. The agreement between theory and experiment has been found to be satisfactory, thus indicating that the open-shell TDDFT (F. Wang and T. Ziegler, Mol. Phys., 2004, 102, 2585) may be used with some confidence to look into the X-ray absorption spectroscopy results pertinent to transition metal complexes. As far as the metal-ligand interaction is concerned, the combined use of NEXAFS spectroscopy and DFT outcomes ultimately testified the significant ionic contribution characterizing the bonding between the metal centre and the nitrogen atoms of the phthalocyanine coordinative pocket.
authors.affiliation: Istituto dei Materiali per l'Elettronica ed il Magnetismo, Consiglio Nazionale delle Ricerche IMEM-CNR, Trento, Italy. marco.nardi@physik.hu-berlin.de
authors.forename: Marco Vittorio
authors.initials: MV
authors.lastname: Nardi
authors.forename: Francesca
authors.initials: F
authors.lastname: Detto
authors.forename: Lucrezia
authors.initials: L
authors.lastname: Aversa
authors.forename: Roberto
authors.initials: R
authors.lastname: Verucchi
authors.forename: Giancarlo
authors.initials: G
authors.lastname: Salviati
authors.forename: Salvatore
authors.initials: S
authors.lastname: Iannotta
authors.forename: Maurizio
authors.initials: M
authors.lastname: Casarin
mesh_terms: D003300:Copper / Q000737:chemistry*; D004583:Electrons; D007211:Indoles / Q000737:chemistry*; D054833:Isoindoles; D009942:Organometallic Compounds / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D007211:Indoles; D054833:Isoindoles; D009942:Organometallic Compounds; D003300:Copper; C013647:phthalocyanine